Quaternized monoazo dyes containing a 6-hydroxy-indazole radical



United States Patent 9 3,121,710 QUATERWIZED MONOAZO DYES CONTAINING Ad-HYDRQXY-INDAZGLE RADICAL Robert Frdric Michel Sureau,Enghien-les-Bains, and

Jean Lon Adrien Rollet, Eaubonne, France, assignors to CompagnieFrangaise des Matieres Colcrantes, Paris,

France, a French company No Drawing. Filed Oct. 2, 1959, Ser. No.843,913

(Ilairns priority, application France (let. 2, 1958 7 Claims. (Cl.260-146) The present invention concerns new basic aZo dyestuffs, aprocess for their preparation and the coloration of fibres therewith. Itparticularly relates to basic monoazo dyestuffs of the general formula:

to their preparation and their application to the dyeing of polyaorylicfibres. In this formula, X represents a hydrogen or chlorine atom, Yrepresents a hydrogen atom or an alkyl radical, A represents a mineralor a strong organic anionic radical and Z represents the residue of adiazotizable primary aromatic or heterocyclic amine. The latter residuemay be substituted by halogen atoms and/ or by non-solubilising groupssuch as nitno, acylamino, tnifluoromethyl, .alkyl, alkox monoordi-alkylamino, sulphonamido or carbonamido groups. The strong organicanionic radical may be for example the chloroacetyl or tiichloroacetylradical.

The dyestutls of Formula I may be obtained for example by the action, inan organic solvent medium, of an alkyl halide, sulphate orarylsulphonate on a dyestuff of the formula:

N// ha E f (II) in which X, Y and Z have the same significance as above,dissolving the precipitate formed in hot water, filtering andprecipitating the quaternary dyestuff of the Formula I by means of saltor in the form of a product of addition of the compound of Formula Iwith zinc chloride, by means of zinc chloride and salt.

It has been found that the dyestuffs of Formula I or their additioncompounds with zinc chloride are generally very soluble in water andhave an excellent afiinity for tanned cotton, silk, leather andpolyacrylic fibres. The colours obtained, in the range of yellows,oranges and reds, are generally endowed with excellent fastness,especially to washing and to light.

The invention will be more clearly understood by reference to thefollowing examples which are purely illustrative and in which the pantsare by weight unless the contnary is indicated.

Example 1 10.7 parts of orthotoluidine are dissolved in 200 par-ts ofWater by the addition of 25 parts by volume of 30% hydrochloric acid.Diazotization is effected at about C., with a solution of 6.9 parts ofsodium nitrite in 50 3,121,710 Patented Feb. 18, 1964 parts of water.The solution of the diazo compound is then added to a solution of 13.4parts of o-hydroxyvolume of soda lye at 400 g. per litre. The dyestufirapidly precipitates. After 4 hours agitation, hydrochloric acid isadded until an acid reaction on Congo red paper is obtained, and themixture is left under agitation for a further half hour. The dyestuif isfiltered off, washed with water and dried.

This dyestuff is then dissolved at the boil in 2000 parts of dry chloiobenzene. 4 parts of calcined magnesia are added and then, gradually, amixture comprising 250 parts of dry chlorobenzene and 50 parts ofpara-toluenemethyl-sulphon-ate, and the whole is allowed to boil underreflux for 2 hours. After cooling, the new dyestulf is filtered off,washed with ether and dried. A yellow powder, soluble in water, isobtained, which dyes polyacrylic fibres such as that sold under theregistered trademark Orion a bright and full-bodied golden yellow shade,endowed with very good general fastness.

Example 2 15.7 parts of 4-chlcro-2-amino-anisole are dissolved in 200parts of water by the addition of 25 parts by volume of 30% hydrochloricacid, and diazotized at about 5 C., with a solution of 6.9 parts ofsodium nitrite in 50 parts of water. The solution of the diazo compoundis then added to a solution of 13 .4 parts of G-hydroxydndazole in 500parts of Water containing 40 parts by volume of soda lye at 400 g. perlitre. The dyestufi is precipitated. Ait'ter 4 hours agitation,hydrochloric acid is added until an acid reaction on Congo red paper isobtained, and the mixture is again agitated for half an hour. Thedyestuff is filtered oil, washed with water and dried, and is in theform of an orange powder.

This dyestull is dissolved at boiling point in 2000- parts of drychlorobenzene. 4 parts of magnesia are added and then, gradually, amixture comprising 250 parts of dry chlorobenzene and 25 parts by volumeof neutral methyl sulphate, and the whole is allowed to boil underreflux for 2 hours. After cooling, it is filtered to remove the solventand the dyestuff which has precipitated is dissolved in 1000 parts offairly hot water in order to purify it. The solution is filtered, andafter cooling, 10 parts of zinc chloride are added. The precipitate iswashed with a little ice water, drained and dried in an oven at 70 C.The new dyestuil is in the form of a redbrown powder, soluble in water,which dyes Orlon an orange shade endowed with very good fastness tolight and to Washing.

The following table summarises further examples analogous to Examples 1and 2.

Coupling com- Shade on Example Dlazotized amine pound polyacrylic Fibres3 aniline 6-hydroxyyellow.

indazole. 4 m-toluidine do golden yellow. p-toluidine do Do. oanisidine.orange. p-anisidinc Do. o-phenetidin D0. p-phcnetidine Do. o-nitranilineorange.

yellow m-nitraniline yellow. p-nitranilineorange. o-chloraniline goldenyellow mehloranillne. yellow. p-chloraniliue golden yellow 4-chloro2-aminotoluene do Do. 5-chl0ro-2-aminotoluenc 18fi-chloro-2-aminotoluene 19 2,5'diehloro-aniline do Do. 202,5din1ethoxy-anilin do Do.

Coupling com- Shade on Example Diazotlzed amine pound poleyacrylicFibres 2,4-dimethyl-aniline 6-hydr0xyorange.

indazole 2,5-dimethyl-aniline do orange yellow.rn-trifluoromethylaniline d yellow. 4-nitro-2-amino-anisole do orangeyellow. -nitro-2-arnino-anis0le do orange. 3-nitrot-amino-aniso1e"scarlet. 4-nitro-2-amino-toluene yellow.

5nitro-2-amino-toluene" golden yellow. 29 3-amino-4-meth0Xy-benz- .doyellow.

amide. aniline rn-sulphonamide do Do. aniline p-sulphonalnide do goldenyellow m-nitraniline 5-chloro-6-hyyellow.

droxy-indazole. 33 i-ehloro-z-arnino-anisole do scarlet. 34m-nitraniline 2-methyl-6-hyyellow droxy-indarole.

We claim: 1. Monoazo dyestufls of the general formula:

OH X 6B ZN=N GHQ-N on A in which X represents a member selected from thegroup consisting of the hydrogen and chlorine atoms, Y repres'ents amember selected from the group consisting of the hydrogen atom and themethyl radical, Z represents a phenyl radical which may be substitutedby members selected from the group consisting of the chlorine atom andthe methyl, methoxy, ethoxy, nitro, trifluoromethyl, carbonamido, andsulphonamido radicals, A represents a member selected from the groupconsistting of the chlorine atom, the monomethylsulphate radical and thep.toluenesulphonate radical.

2. Addition compounds of zinc chloride with monoazo dyestuffs of thegeneral formula:

in which X represents a member selected from the group consisting of thehydrogen and chlorine atoms, Y represents a member selected from thegroup consisting of the hydrogen atom and the methyl radical, Zrepresents aphenyl radical which may be substituted by members selectedfrom the group consisting of the chlorine atom and the methyl, methoxy,ethoXy, nitro, trifluoromethyl, carbonamido and sulphonarnido radicals,A represents a member selected from the group consisting of the chlorineatom, the monornethylsulphate radical and the p.toluenesulphonateradical.

3. Monoazo dyestuif of the general formula given in claim 1 in which Zrepresents the residue of 4 chloro-2- aminoanisole, X and Y eachrepresent hydrogen atoms, and A represents the monomethyl sulphateradical.

4. Monoazo dyestuif of the general formula given in clairnl in which Zrepresents the residue of matoluidine, X and Y each represent hydrogenatoms, and A repre sents the monomethyl sulphate radical.

5. Monoazo dyestuii of the general formula given in claim l in which Zrepresents the residue of p-chloraniline, X and Y each representhydrogen atoms, and A represents the monomethyl sulphate radical.

6. Monoazo dyest-ufi of the general formula given in claim 1 in which Zrepresents the residue of 4-chloro-2- amino-toluene, X and Y eachrepresent hydrogen atoms, and A represents the monorn'ethyl sulphateradical.

7. Monoazo dyestuif of the general formula given in claim 1 in which Zrepresents the residue of 5-chloro-2- amino, toluene, X and Y eachrepresent hydrogen atoms, and A represents the monomethyl sulphateradical.

References Cited in the file of this patent UNITED STATES PATENTS2,448,870 Dickey et al. Sept. 7, 1948 2,475,506 Lewis July 5, 19492,717,823 Lowe Sept. 13, 1955 2,828,301 Sureau et a1 Mar. 25, 19582,883,373 Bossard et al Apr. 21, 1959 2,889,315 Bossard et al June 2,1959 2,893,816 'Isang et a1. July 7, 1959

1. MONOAZO DYESTUFFS OF THE GENERAL FORMULA: